Estudo da combust��o do ��leo pirol��tico de pneus

Coordena����o de Aperfei��oamento de Pessoal de N��vel Superior (CAPES)

Association of genetic variants in the promoter region of genes encoding p22phox (CYBA) and glutamate cysteine ligase catalytic subunit (GCLC) and renal disease in patients with type 1 diabetes mellitus

Background Oxidative stress is recognized as a major pathogenic factor of cellular damage caused by hyperglycemia. NOX/NADPH oxidases generate reactive oxygen species and NOX1, NOX2 and NOX4 isoforms are expressed in kidney and require association with subunit p22phox (encoded by the CYBA gene). Increased expression of p22phox was described in animal models of diabetic nephropathy. In the opposite direction, glutathione is one of the main endogenous antioxidants whose plasmatic concentrations were reported to be reduced in diabetes patients. The aim of the present investigation was to test whether functional single nucleotide polymorphisms (SNPs) in genes involved in the generation of NADPH-dependent O2���- (-675 T ��� A in CYBA, unregistered) and in glutathione metabolism (-129 C ��� T in GCLC [rs17883901] and -65 T ��� C in GPX3 [rs8177412]) confer susceptibility to renal disease in type 1 diabetes patients. Methods 401 patients were sorted into two groups according to the presence (n = 104) or absence (n = 196) of overt diabetic nephropathy or according to glomerular filtration rate (GFR) estimated by Modification of Diet in Renal Disease (MDRD) equation: ��� 60 mL (n = 265) or < 60 mL/min/1.73 m2 (n = 136) and were genotyped. Results No differences were found in the frequency of genotypes between diabetic and non-diabetic subjects. The frequency of GFR < 60 mL/min was significantly lower in the group of patients carrying CYBA genotypes T/A+A/A (18.7%) than in the group carrying the T/T genotype (35.3%) (P = 0.0143) and the frequency of GFR < 60 mL/min was significantly higher in the group of patients carrying GCLC genotypes C/T+T/T (47.1%) than in the group carrying the C/C genotype (31.1%) (p = 0.0082). Logistic regression analysis identified the presence of at least one A allele of the CYBA SNP as an independent protection factor against decreased GFR (OR = 0.38, CI95% 0.14-0.88, p = 0.0354) and the presence of at least one T allele of the GCLC rs17883901 SNP as an independent risk factor for decreased GFR (OR = 2.40, CI95% 1.27-4.56, p = 0.0068). Conclusions The functional SNPs CYBA -675 T ��� A and GCLC rs17883901, probably associated with cellular redox imbalances, modulate the risk for renal disease in the studied population of type 1 diabetes patients and require validation in additional cohorts.

Development of plurimetallic electrocatalysts prepared by decomposition of polymeric precursors for EtOH/O2 fuel cell

This work aimed to develop plurimetallic electrocatalysts composed of Pt, Ru, Ni, and Sn supported on C by decomposition of polymeric precursors (DPP), at a constant metal:carbon ratio of 40:60 wt.%, for application in direct ethanol fuel cell (DEFC). The obtained nanoparticles were physico-chemically characterized by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX). XRD results revealed a face-centered cubic crystalline Pt with evidence that Ni, Ru, and Sn atoms were incorporated into the Pt structure. Electrochemical characterization of the nanoparticles was accomplished by cyclic voltammetry (CV) and chronoamperometry (CA) in slightly acidic medium (0.05 mol L-1 H2SO4), in the absence and presence of ethanol. Addition of Sn to PtRuNi/C catalysts significantly shifted the ethanol and CO onset potentials toward lower values, thus increasing the catalytic activity, especially for the quaternary composition Pt64Sn15Ru13Ni8/C. Electrolysis of ethanol solutions at 0.4 V vs. RHE allowed determination of acetaldehyde and acetic acid as the main reaction products. The presence of Ru in alloys promoted formation of acetic acid as the main product of ethanol oxidation. The Pt64Sn15Ru13Ni8/C catalyst displayed the best performance for DEFC.

Effects of ATP-induced leg vasodilation on VO2 peak and leg O2 extraction during maximal exercise in humans

[EN] During maximal whole body exercise VO2 peak is limited by O2 delivery. In turn, it is though that blood flow at near-maximal exercise must be restrained by the sympathetic nervous system to maintain mean arterial pressure. To determine whether enhancing vasodilation across the leg results in higher O2 delivery and leg VO2 during near-maximal and maximal exercise in humans, seven men performed two maximal incremental exercise tests on the cycle ergometer. In random order, one test was performed with and one without (control exercise) infusion of ATP (8 mg in 1 ml of isotonic saline solution) into the right femoral artery at a rate of 80 microg.kg body mass-1.min-1. During near-maximal exercise (92% of VO2 peak), the infusion of ATP increased leg vascular conductance (+43%, P<0.05), leg blood flow (+20%, 1.7 l/min, P<0.05), and leg O2 delivery (+20%, 0.3 l/min, P<0.05). No effects were observed on leg or systemic VO2. Leg O2 fractional extraction was decreased from 85+/-3 (control) to 78+/-4% (ATP) in the infused leg (P<0.05), while it remained unchanged in the left leg (84+/-2 and 83+/-2%; control and ATP; n=3). ATP infusion at maximal exercise increased leg vascular conductance by 17% (P<0.05), while leg blood flow tended to be elevated by 0.8 l/min (P=0.08). However, neither systemic nor leg peak VO2 values where enhanced due to a reduction of O2 extraction from 84+/-4 to 76+/-4%, in the control and ATP conditions, respectively (P<0.05). In summary, the VO2 of the skeletal muscles of the lower extremities is not enhanced by limb vasodilation at near-maximal or maximal exercise in humans. The fact that ATP infusion resulted in a reduction of O2 extraction across the exercising leg suggests a vasodilating effect of ATP on less-active muscle fibers and other noncontracting tissues and that under normal conditions these regions are under high vasoconstrictor influence to ensure the most efficient flow distribution of the available cardiac output to the most active muscle fibers of the exercising limb.

Muscular and pulmonary O2 uptake kinetics during moderate- and high-intensity sub-maximal knee-extensor exercise in humans

[EN] The purpose of this investigation was to determine the contribution of muscle O(2) consumption (mVO2) to pulmonary O(2) uptake (pVO2) during both low-intensity (LI) and high-intensity (HI) knee-extension exercise, and during subsequent recovery, in humans. Seven healthy male subjects (age 20-25 years) completed a series of LI and HI square-wave exercise tests in which mVO2 (direct Fick technique) and pVO2 (indirect calorimetry) were measured simultaneously. The mean blood transit time from the muscle capillaries to the lung (MTTc-l) was also estimated (based on measured blood transit times from femoral artery to vein and vein to artery). The kinetics of mVO2 and pVO2 were modelled using non-linear regression. The time constant (tau) describing the phase II pVO2 kinetics following the onset of exercise was not significantly different from the mean response time (initial time delay + tau) for mVO2 kinetics for LI (30 +/- 3 vs 30 +/- 3 s) but was slightly higher (P < 0.05) for HI (32 +/- 3 vs 29 +/- 4 s); the responses were closely correlated (r = 0.95 and r = 0.95; P < 0.01) for both intensities. In recovery, agreement between the responses was more limited both for LI (36 +/- 4 vs 18 +/- 4 s, P < 0.05; r = -0.01) and HI (33 +/- 3 vs 27 +/- 3 s, P > 0.05; r = -0.40). MTTc-l was approximately 17 s just before exercise and decreased to 12 and 10 s after 5 s of exercise for LI and HI, respectively. These data indicate that the phase II pVO2 kinetics reflect mVO2 kinetics during exercise but not during recovery where caution in data interpretation is advised. Increased mVO2 probably makes a small contribution to during the first 15-20 s of exercise.

Air to muscle O2 delivery during exercise at altitude

[EN] Hypoxia-induced hyperventilation is critical to improve blood oxygenation, particularly when the arterial Po2 lies in the steep region of the O2 dissociation curve of the hemoglobin (ODC). Hyperventilation increases alveolar Po2 and, by increasing pH, left shifts the ODC, increasing arterial saturation (Sao2) 6 to 12 percentage units. Pulmonary gas exchange (PGE) is efficient at rest and, hence, the alveolar-arterial Po2 difference (Pao2-Pao2) remains close to 0 to 5mm Hg. The (Pao2-Pao2) increases with exercise duration and intensity and the level of hypoxia. During exercise in hypoxia, diffusion limitation explains most of the additional Pao2-Pao2. With altitude, acclimatization exercise (Pao2-Pao2) is reduced, but does not reach the low values observed in high altitude natives, who possess an exceptionally high DLo2. Convective O2 transport depends on arterial O2 content (Cao2), cardiac output (Q), and muscle blood flow (LBF). During whole-body exercise in severe acute hypoxia and in chronic hypoxia, peak Q and LBF are blunted, contributing to the limitation of maximal oxygen uptake (Vo2max). During small-muscle exercise in hypoxia, PGE is less perturbed, Cao2 is higher, and peak Q and LBF achieve values similar to normoxia. Although the Po2 gradient driving O2 diffusion into the muscles is reduced in hypoxia, similar levels of muscle O2 diffusion are observed during small-mass exercise in chronic hypoxia and in normoxia, indicating that humans have a functional reserve in muscle O2 diffusing capacity, which is likely utilized during exercise in hypoxia. In summary, hypoxia reduces Vo2max because it limits O2 diffusion in the lung.

Effects of recovery mode on performance, O2 uptake, and O2 deficit during high-intensity intermittent exercise

[EN] The aim of this study was to determine the influence of activity performed during the recovery period on the aerobic and anaerobic energy yield, as well as on performance, during high-intensity intermittent exercise (HIT). Ten physical education students participated in the study. First they underwent an incremental exercise test to assess their maximal power output (Wmax) and VO2max. On subsequent days they performed three different HITs. Each HIT consisted of four cycling bouts until exhaustion at 110% Wmax. Recovery periods of 5 min were allowed between bouts. HITs differed in the kind of activity performed during the recovery periods: pedaling at 20% VO2max (HITA), stretching exercises, or lying supine. Performance was 3-4% and aerobic energy yield was 6-8% (both p < 0.05) higher during the HITA than during the other two kinds of HIT. The greater contribution of aerobic metabolism to the energy yield during the high-intensity exercise bouts with active recovery was due to faster VO2 kinetics (p< 0.01) and a higher VO2peak during the exercise bouts preceded by active recovery (p < 0.05). In contrast, the anaerobic energy yield (oxygen deficit and peak blood lactate concentrations) was similar in all HITs. Therefore, this study shows that active recovery facilitates performance by increasing aerobic contribution to the whole energy yield turnover during high-intensity intermittent exercise.

Effect of blood haemoglobin concentration on V(O2,max) and cardiovascular function in lowlanders acclimatised to 5260 m

[EN] The principal aim of this investigation was to determine the influence of blood haemoglobin concentration ([Hb]) on maximal exercise capacity and maximal O(2) consumption (V(O(2),max)) in healthy subjects acclimatised to high altitude. Secondarily, we examined the effects of [Hb] on the regulation of cardiac output (CO), blood pressure and muscular blood flow (LBF) during exercise. Eight Danish lowlanders (three females and five males; 24 +/- 0.6 years, mean +/- S.E.M.) performed submaximal and maximal exercise on a cycle ergometer after 9 weeks at an altitude of 5260 m (Mt Chacaltaya, Bolivia). This was done first with the high [Hb] resulting from acclimatisation and again 2-4 days later, 1 h after isovolaemic haemodilution with Dextran 70 to near sea level [Hb]. After measurements at maximal exercise while breathing air at each [Hb], subjects were switched to hyperoxia (55 % O(2) in N(2)) and the measurements were repeated, increasing the work rate as tolerated. Hyperoxia increased maximal power output and leg V(O(2),max), showing that breathing ambient air at 5260 m, V(O(2),max) is limited by the availability of O(2) rather than by muscular oxidative capacity. Altitude increased [Hb] by 36 % from 136 +/- 5 to 185 +/- 5 g l(-1) (P < 0.001), while haemodilution (replacing 1 l of blood with 1 l of 6 % Dextran) lowered [Hb] by 24 % to 142 +/- 6 g l(-1) (P < 0.001). Haemodilution had no effect on maximal pulmonary or leg V(O(2),max), or power output. Despite higher LBF, leg O(2) delivery was reduced and maximal V(O(2)) was thus maintained by higher O(2) extraction. While CO increased linearly with work rate irrespective of [Hb] or inspired oxygen fraction (F(I,O(2))), both LBF and leg vascular conductance were systematically higher when [Hb] was low. Close and significant relationships were seen between LBF (and CO) and both plasma noradrenaline and K(+) concentrations, independently of [Hb] and F(I,O(2)). In summary, under conditions where O(2) supply limits maximal exercise, the increase in [Hb] with altitude acclimatisation does not improve maximal exercise capacity or V(O(2),max), and does not alter peak CO. However, LBF and vascular conductance are higher at altitude when [Hb] is lowered to sea level values, with both relating closely to catecholamine and potassium concentrations. This suggests that the lack of effect of [Hb] on V(O(2),max) may involve reciprocal changes in LBF via local metabolic control of the muscle vasculature.

Why is VO2 max after altitude acclimatization still reduced despite normalization of arterial O2 content?

[EN] Acute hypoxia (AH) reduces maximal O2 consumption (VO2 max), but after acclimatization, and despite increases in both hemoglobin concentration and arterial O2 saturation that can normalize arterial O2 concentration ([O2]), VO2 max remains low. To determine why, seven lowlanders were studied at VO2 max (cycle ergometry) at sea level (SL), after 9-10 wk at 5,260 m [chronic hypoxia (CH)], and 6 mo later at SL in AH (FiO2 = 0.105) equivalent to 5,260 m. Pulmonary and leg indexes of O2 transport were measured in each condition. Both cardiac output and leg blood flow were reduced by approximately 15% in both AH and CH (P < 0.05). At maximal exercise, arterial [O2] in AH was 31% lower than at SL (P < 0.05), whereas in CH it was the same as at SL due to both polycythemia and hyperventilation. O2 extraction by the legs, however, remained at SL values in both AH and CH. Although at both SL and in AH, 76% of the cardiac output perfused the legs, in CH the legs received only 67%. Pulmonary VO2 max (4.1 +/- 0.3 l/min at SL) fell to 2.2 +/- 0.1 l/min in AH (P < 0.05) and was only 2.4 +/- 0.2 l/min in CH (P < 0.05). These data suggest that the failure to recover VO2 max after acclimatization despite normalization of arterial [O2] is explained by two circulatory effects of altitude: 1) failure of cardiac output to normalize and 2) preferential redistribution of cardiac output to nonexercising tissues. Oxygen transport from blood to muscle mitochondria, on the other hand, appears unaffected by CH.

Arterial O2 content and tension in regulation of cardiac output and leg blood flow during exercise in humans

[EN] A universal O2 sensor presumes that compensation for impaired O2 delivery is triggered by low O2 tension, but in humans, comparisons of compensatory responses to altered arterial O2 content (CaO2) or tension (PaO2) have not been reported. To directly compare cardiac output (QTOT) and leg blood flow (LBF) responses to a range of CaO2 and PaO2, seven healthy young men were studied during two-legged knee extension exercise with control hemoglobin concentration ([Hb] = 144.4 +/- 4 g/l) and at least 1 wk later after isovolemic hemodilution ([Hb] = 115 +/- 2 g/l). On each study day, subjects exercised twice at 30 W and on to voluntary exhaustion with an FIO2 of 0.21 or 0.11. The interventions resulted in two conditions with matched CaO2 but markedly different PaO2 (hypoxia and anemia) and two conditions with matched PaO2 and different CaO2 (hypoxia and anemia + hypoxia). PaO2 varied from 46 +/- 3 Torr in hypoxia to 95 +/- 3 Torr (range 37 to >100) in anemia (P < 0.001), yet LBF at exercise was nearly identical. However, as CaO2 dropped from 190 +/- 5 ml/l in control to 132 +/- 2 ml/l in anemia + hypoxia (P < 0.001), QTOT and LBF at 30 W rose to 12.8 +/- 0.8 and 7.2 +/- 0.3 l/min, respectively, values 23 and 47% above control (P < 0.01). Thus regulation of QTOT, LBF, and arterial O2 delivery to contracting intact human skeletal muscle is dependent for signaling primarily on CaO2, not PaO2. This finding suggests that factors related to CaO2 or [Hb] may play an important role in the regulation of blood flow during exercise in humans.

Sviluppi di catalizzatori per l'abbattimento di NOx in presenza di ossigeno

Il traffico veicolare �� la principale fonte antropogenica di NOx, idrocarburi (HC) e CO e, dato che la sostituzione dei motori a combustione interna con sistemi alternativi appare ancora lontana nel tempo, lo sviluppo di sistemi in grado di limitare al massimo le emissioni di questi mezzi di trasporto riveste un���importanza fondamentale. Sfortunatamente non esiste un rapporto ottimale aria/combustibile che permetta di avere basse emissioni, mentre la massima potenza ottenibile dal motore corrisponde alle condizioni di elevata formazione di CO e HC. Gli attuali sistemi di abbattimento permettono il controllo delle emissioni da sorgenti mobili tramite una centralina che collega il sistema di iniezione del motore e la concentrazione di ossigeno del sistema catalitico (posto nella marmitta) in modo da controllare il rapporto aria/combustibile (Fig. 1). Le marmitte catalitiche per motori a benzina utilizzano catalizzatori ���three way��� a base di Pt/Rh supportati su ossidi (allumina, zirconia e ceria), che, dovendo operare con un rapporto quasi stechiometrico combustibile/comburente, comportano una minore efficienza del motore e consumi maggiori del 20-30% rispetto alla combustione in eccesso di ossigeno. Inoltre, questa tecnologia non pu�� essere utilizzata nei motori diesel, che lavorano in eccesso di ossigeno ed utilizzano carburanti con un tenore di zolfo relativamente elevato. In questi ultimi anni �� cresciuto l���interesse per il controllo delle emissioni di NOx da fonti veicolari, con particolare attenzione alla riduzione catalitica in presenza di un eccesso di ossigeno, cio�� in condizioni di combustione magra. Uno sviluppo recente �� rappresentato dai catalizzatori tipo ���Toyota��� che sono basati sul concetto di accumulo e riduzione (storage/reduction), nei quali l���NO viene ossidato ed accumulato sul catalizzatore come nitrato in condizioni di eccesso di ossigeno. Modificando poi per brevi periodi di tempo le condizioni di alimentazione da ossidanti (aria/combustibile > 14,7 p/p) a riducenti (aria/combustibile < 14,7 p/p) il nitrato immagazzinato viene ridotto a N2 e H2O. Questi catalizzatori sono per�� molto sensibili alla presenza di zolfo e non possono essere utilizzati con i carburanti diesel attualmente in commercio. Obiettivo di questo lavoro di tesi �� stato quello di ottimizzare e migliorare la comprensione del meccanismo di reazione dei catalizzatori ���storage-reduction��� per l���abbattimento degli NOx nelle emissioni di autoveicoli in presenza di un eccesso di ossigeno. In particolare lo studio �� stato focalizzato dapprima sulle propriet�� del Pt, fase attiva nei processi di storage-reduction, in funzione del tipo di precursore e sulle propriet�� e composizione della fase di accumulo (Ba, Mg ed una loro miscela equimolare) e del supporto (��-Al2O3 o Mg(Al)O). Lo studio �� stato inizialmente focalizzato sulle propriet�� dei precursori del Pt, fase attiva nei processi di storage-reduction, sulla composizione della fase di accumulo (Ba, Mg ed una loro miscela equimolare) e del supporto (��-Al2O3 o Mg(Al)O). E��� stata effettuata una dettagliata caratterizzazione chimico-fisica dei materiali preparati tramite analisi a raggi X (XRD), area superficiale, porosimetria, analisi di dispersione metallica, analisi in riduzione e/o ossidazione in programmata di temperatura (TPR-O), che ha permesso una migliore comprensione delle propriet�� dei catalizzatori. Vista la complessit�� delle miscele gassose reali, sono state utilizzate, nelle prove catalitiche di laboratorio, alcune miscele pi�� semplici, che tuttavia potessero rappresentare in maniera significativa le condizioni reali di esercizio. Il comportamento dei catalizzatori �� stato studiato utilizzando differenti miscele sintetiche, con composizioni che permettessero di comprendere meglio il meccanismo. L���intervallo di temperatura in cui si �� operato �� compreso tra 200-450��C. Al fine di migliorare i catalizzatori, per aumentarne la resistenza alla disattivazione da zolfo, sono state effettuate prove alimentando in continuo SO2 per verificare la resistenza alla disattivazione in funzione della composizione del catalizzatore. I principali risultati conseguiti possono essere cos�� riassunti: A. Caratteristiche Fisiche. Dall���analisi XRD si osserva che l���impregnazione con Pt(NH3)2(NO2)2 o con la sospensione nanoparticellare in DEG, non modifica le propriet�� chimico-fisiche del supporto, con l���eccezione del campione con sospensione nanoparticellare impregnata su ossido misto per il quale si �� osservata sia la segregazione del Pt, sia la presenza di composti carboniosi sulla superficie. Viceversa l���impregnazione con Ba porta ad una significativa diminuzione dell���area superficiale e della porosit��. B. Caratteristiche Chimiche. L���analisi di dispersione metallica, tramite il chemiassorbimento di H2, mostra per i catalizzatori impregnati con Pt nanoparticellare, una bassa dispersione metallica e di conseguenza elevate dimensioni delle particelle di Pt. I campioni impregnati con Pt(NH3)2(NO2)2 presentano una migliore dispersione. Infine dalle analisi TPR-O si �� osservato che: Maggiore �� la dispersione del metallo nobile maggiore �� la sua interazione con il supporto, L���aumento della temperatura di riduzione del PtOx �� proporzionale alla quantit�� dei metalli alcalino terrosi, C. Precursore Metallo Nobile. Nelle prove di attivit�� catalitica, con cicli ossidanti e riducenti continui in presenza ed in assenza di CO2, i catalizzatori con Pt nanoparticellare mostrano una minore attivit�� catalitica, specie in presenza di un competitore come la CO2. Al contrario i catalizzatori ottenuti per impregnazione con la soluzione acquosa di Pt(NH3)2(NO2)2 presentano un���ottima attivit�� catalitica, stabile nel tempo, e sono meno influenzabili dalla presenza di CO2. D. Resistenza all���avvelenamento da SO2. Il catalizzatore di riferimento, 17Ba1Pt/��Al2O3, mostra un effetto di avvelenamento con formazione di solfati pi�� stabili che sul sistema Ba-Mg; difatti il campione non recupera i valori iniziali di attivit�� se non dopo molti cicli di rigenerazione e temperature superiori ai 300��C. Per questi catalizzatori l���avvelenamento da SO2 sembra essere di tipo reversibile, anche se a temperature e condizioni pi�� favorevoli per il 1.5Mg8.5Ba-1Pt/��Al2O3. E. Capacit�� di Accumulo e Rigenerabilit��. Tramite questo tipo di prova �� stato possibile ipotizzare e verificare il meccanismo della riduzione. I catalizzatori ottenuti per impregnazione con la soluzione acquosa di Pt(NH3)2(NO2)2 hanno mostrato un���elevata capacit�� di accumulo. Questa �� maggiore per il campione bimetallico (Ba-Mg) a T < 300��C, mentre per il riferimento �� maggiore per T > 300��C. Per ambedue i catalizzatori �� evidente la formazione di ammoniaca, che potrebbe essere utilizzata come un indice che la riduzione dei nitrati accumulati �� arrivata al termine e che il tempo ottimale per la riduzione �� stato raggiunto o superato. Per evitare la formazione di NH3, sul catalizzatore di riferimento, �� stata variata la concentrazione del riducente e la temperatura in modo da permettere alle specie adsorbite sulla superficie e nel bulk di poter raggiungere il Pt prima che l���ambiente diventi troppo riducente e quindi meno selettivo. La presenza di CO2 riduce fortemente la formazione di NH3; probabilmente perch�� la CO2, occupando i siti degli elementi alcalino-terrosi lontani dal Pt, impedisce ai nitriti/nitrati o all���H2 attivato di percorrere ���elevate��� distanze prima di reagire, aumentando cos�� le possibilit�� di una riduzione pi�� breve e pi�� selettiva. F. Tempo di Riduzione. Si �� migliorata la comprensione del ruolo svolto dalla concentrazione dell���agente riducente e dell���effetto della durata della fase riducente. Una durata troppo breve porta, nel lungo periodo, alla saturazione dei siti attivi, un eccesso alla formazione di NH3 Attraverso queste ultime prove �� stato possibile formulare un meccanismo di reazione, in particolare della fase riducente. G. Meccanismo di Riduzione. La mobilit�� dei reagenti, nitriti/nitrati o H2 attivato �� un elemento fondamentale nel meccanismo della riduzione. La vicinanza tra i siti di accumulo e quelli redox �� determinante per il tipo di prodotti che si possono ottenere. La diminuzione della concentrazione del riducente o l���aumento della temperatura concede maggiore tempo o energia alle specie adsorbite sulla superficie o nel bulk per migrare e reagire prima che l���ambiente diventi troppo riducente e quindi meno selettivo.

Untersuchung zur Temperaturabh��ngigkeit der O2-Bindungseigenschaft von H��mocyanin aus Arthropoden verschiedener Biotope

Die Evolution hat nur wenige O2-Transportproteine im Tierreich hervorgebracht. Sie alle nutzen entweder die Metallionen Fe2+ oder Cu2+ zur reversiblen Sauerstoffbindung in vier verschiedenen Typen von aktiven Zentren. Die Metallatome werden dabei ��ber eine prosthetische Gruppe (Porphyrin-Ring) oder direkt (koordinativ) durch Histidine an die Proteinmatrix gebunden. Die Atmungsproteine sorgen f��r den Transport des Sauerstoffs von den respiratorischen Epithelien (Lunge, Kiemen), hin zu den O2 verbrauchenden Gewebszellen (oxidativer Stoffwechsel). Die Beladung mit Sauerstoff in den Lungen, bzw. den Kiemen sollte leicht und schnell, d.h. mit einer m��glichst hohen O2-Affinit��t erfolgen. Die Arthropoden sind ein sehr artenreicher und erfolgreicher Tierstamm. Ihnen ist es im Laufe der Evolution gelungen, fast alle Lebensr��ume zu Wasser, auf dem Land und in der Luft zu besiedeln. Die Erschlie��ung so unterschiedlicher Biotope setzt eine sehr gute physiologische Anpassungsf��higkeit voraus. Das physiologisch wichtigste Problem, welches f��r jeden Lebensraum w��hrend der Evolution gel��st werden mu��te, ist eine optimale Sauerstoffversorgung der K��rperzellen bei allen Umweltbedingungen zu gew��hrleisten. Ziel dieser Arbeit war es zu untersuchen, inwieweit verschiedene Arthropoden-H��mocyanine eine biotopabh��ngige (temperaturabh��ngige) Adaptation der O2-Versorgung (Proteinfunktion) auf Ebene des H��mocyaninmolek��ls zeigen. Bei den hier untersuchten H��mocyaninen lie�� sich eine signifikante Biotopabh��ngigkeit f��r den ���Proteinfunktions-Parameter��� Kooperativit��t nachweisen.